Due to the special relevance of the invention for pressure measurement cells, the invention will first be explained based on pressure measurement cells.
Pressure measurement cells according to the state of the art combine a ceramic measuring membrane and a ceramic platform, wherein the measuring membrane is connected pressure-tightly with the platform along a peripheral joint, which contains an active hard solder, or braze, wherein a pressure chamber is formed between the measuring membrane and the platform, wherein the equilibrium position of the measuring membrane results from the difference between a pressure reigning in the pressure chamber and a pressure acting on the outside of the measuring membrane facing away from the pressure chamber.
Serving as material for the platform and the measuring membrane are especially aluminum oxide ceramics, which, due to their elastic properties and their media resistance, are suited for manufacture of pressure measurement cells. The mentioned ceramic components are especially joined with an active hard solder, or braze, which is preferably an active hard solder, or braze containing Zr, Ni and Ti. The manufacture of such an active hard solder, or braze, is disclosed, for example, in European Offenlegungsschrift (laid open application) EP 0 490 807 A2. According to the method described there, especially rings of the active braze material can be manufactured, which are positioned between measuring membrane and platform, in order to solder, or braze, these with one another.
The molten active hard solder, or braze, tends, however, to flow radially inwards. Thus, additional measures are required, in order to avoid this. In this regard, for example, Offenlegungsschrift (laid open application) DE 100 36 433 AI discloses a capacitive pressure measuring cell, which likewise has a joint with an active hard solder, or braze, wherein at the joint root, thus the inner radius of the joint, a ring-shaped surrounding groove is formed, which, on the one hand, prevents localized stress concentrations at the joint and, on the other hand, defines a reliable solder stop, via which the active hard solder, or braze cannot flow further radially inwards.
A practiced method for limiting the radially inwards flowing of active hard solder, or braze involves oxidizing the surface of a membrane-side electrode, which contains tantalum, and which is intended for galvanic contact with the active hard solder, or braze. At relatively low solder temperatures, this can prevent a running of the active hard solder, or braze, into the pressure chamber and provides an acceptable yield. When, however, the soldering temperature is increased, this solder stop is no longer reliable, and the solder flows over the edge of the tantalum electrode into the pressure chamber.
In the yet unpublished patent application DE 10 2012 103 166, a graphite layer is disclosed as solder stop.
Defects in the graphite layer can, however, in given cases, degrade the wetting prevention. It is, therefore, an object of the present invention to provide an assembly, respectively a pressure measuring cell, in whose manufacture a flowing of the solder past a solder stop is reliably prevented.
The object is achieved according to the invention by the assembly which includes a first ceramic body and a second ceramic body, wherein the first ceramic body and the second ceramic body are connected by means of a joint, wherein the joint contains an active hard solder, or braze, wherein the active hard solder, or braze, averaged over a continuous main volume, which includes at least 50%, especially at least 70% and preferably at least 80%, of the volume of the joint, has an average composition CM with a liquidus temperature Tl(CM), wherein CM:=(cM1, . . . , cMN), wherein |CM|=1, and wherein the cMi are the stoichiometric fractions of the components Ki=1, . . . , N of the average composition of the active hard solder, or braze in the main volume, wherein according to the invention an edge region of the joint, which contacts at least one of the ceramic bodies, and which overlaps no more than 8% of the main volume, for example, no more than 4% and especially no more than 2% and preferably lies outside of the main volume, has an average composition CE with a liquidus temperature Tl(CE), which lies not less than 20 K, preferably not less than 50 K, and especially preferably not less than 100 K above the liquidus temperature Tl(CM) of the average composition CM of the main volume, wherein CE:=(cE1, . . . , cEN), wherein |CE|=1, and wherein the cEi are the stoichiometric fractions of the components Ki=1, . . . , N of the average composition of the active hard solder, or braze, in the edge region.
In a further development of the invention, the edge region with the average composition CE has a volume, which amounts to not less than 0.1%, for example, not less than 0.5% and especially not less than 1% of the volume of the joint.
In a further development of the invention, the joint is ring-shaped, wherein the main volume is defined by a body of revolution, which is formed by rotation of a convex polygon, especially a rectangle, about the principal axis of rotation of the ring.
In a further development of the invention, the edge region with composition CE extends along the inner edge of the annular joint.
In a further development of the invention, the liquidus temperature of Tl(CM) rises monotonically to the liquidus temperature Tl(CE) with change of composition from CM to CE.
In a further development of the invention, the composition CM has a liquidus temperature Tl(CM), which lies no more than 300 K, preferably no more than 150 K, and preferably no more than 50 K above the liquidus temperature Tl(Ce) of the eutectic point, respectively the nearest intersection with a eutectic valley with a composition Ce in the composition space, wherein Ce:=(ce1, . . . , ceN), wherein |Ce|=1, and wherein the cei are the stoichiometric fractions of the components Ki with i=1, . . . , N at the eutectic point, respectively a nearest intersection with a eutectic valley.
The nearest intersection with a eutectic valley is defined by a point in a eutectic valley, for whose composition Ce it holds that the magnitude of the vector difference |Ce−CM| has a minimum among all points in eutectic valleys.
In a further development of the invention, the alloy of the joint has at the eutectic point, respectively at the nearest intersection with a eutectic valley in the composition space, a composition Ce, wherein Ce:=(ce1, . . . , ceN), wherein |Ce|=1, wherein the cei are the stoichiometric fractions of the components Ki with i=1, . . . , N at the eutectic point, respectively at the nearest intersection with a eutectic valley, wherein the difference between the composition Ce and the composition CM is describable with a normalized vector difference DeM, wherein: Ce=CM+aeM*DeM, with |DeM|=1, wherein the difference between the composition CE and the composition CM is describable with a normalized vector difference DEM, wherein: CE=CM+aEM*DEM, with |DEM|=1, wherein aeM and aEM are positive scalars, wherein for the scalar product seE: =DeM·DEM: seE<0, especially seE<−0.5, preferably seE<−0.8.
In a further development of the invention, the first ceramic body and/or the second ceramic body comprises Al2O3.
In a further development of the invention, the active hard solder, or braze, contains Zr, Ni and Ti, wherein in an embodiment of the invention the active hard solder, or braze, at least in the main volume, is composed of these components and, in given cases, aluminum, which in the soldering process diffuses from the ceramic into the joint.
In an embodiment of this further development of the invention, the composition CM comprises 20 atom-% to 24 atom-% Ni, 13 atom-% to 17 atom-% Ti and remainder Zr, as well as, in given cases, aluminum, which diffuses in the soldering process from the ceramic into the joint, wherein the composition CM especially comprises 63 atom-% Zr, 22 atom-% Ni and 15 atom-% Ti, wherein, in given cases, Al diffuses in, wherein in the cases when Al is present, especially the titanium fraction is reduced, and wherein the composition CE has compared with the composition CM an increased Ni fraction.
In a further development of the invention, the composition CE of the edge region contains the same metals as the composition CM of the main volume. In an embodiment of this further development of the invention, the compositions contain, apart from, in given cases, impurities, no additional elements. In another further development of the invention, the composition of the edge region contains at least one further metal selected from a list, which includes Cu, Fe, Al, Ag and Au.
The pressure measuring cell of the invention comprises an assembly of the invention, wherein the first ceramic body is a membrane body of a measuring membrane of the pressure measuring cell, and wherein the second ceramic body is a platform of the pressure measuring cell, wherein the platform and the measuring membrane are joined pressure-tightly with one another by means of the joint, which is ring-shaped.
In a further development, the pressure measuring cell includes a capacitive transducer, wherein a surface of the platform facing the measuring membrane and/or the surface of the measuring membrane facing the platform have, respectively has, a metal electrode, wherein the electrode comprises a metal, which is enriched in the composition CE in comparison to the composition CM. In a further development of the invention, this metal comprises nickel.
The method of the invention for manufacturing an assembly of a first ceramic body and a second ceramic body, wherein the first ceramic body and the second ceramic body are to be joined by means of an active hard solder, or braze, comprises steps as follows: Providing the active hard solder, or braze, and a solder stop between the ceramic bodies, wherein the active hard solder, or braze, before the soldering, has, averaged over a continuous main volume, which includes at least 50%, especially at least 70% and preferably at least 80% of the volume of the active hard solder, or braze, an average composition CM0 with a liquidus temperature Tl(CM0), wherein CM0:=(cM01, . . . , cM0N), wherein |CM0|=1, and wherein the cM0i are the stoichiometric fractions of the components Ki i=1, . . . , N of the average composition of the active hard solder, or braze, in the main volume, wherein the solder stop has at least one material, whose liquidus temperature lies above the liquidus temperature of the composition CM0 of the main volume, and wherein a mixing of the material of the solder stop with the composition CM0 leads, at least in the edge region of a joint to be formed by the method, to an average composition CE, wherein the composition CE has a liquidus temperature Tl(CE), which lies not less than 20 K, preferably not less than 50 K, and especially preferably not less than 100 K above the liquidus temperature Tl(CM0) of the average composition CM0 of the main volume, wherein CE:=(cE1, . . . , cEN), wherein |CE|=1, and wherein the cEi are the stoichiometric fractions of the components Ki i=1, . . . , N of the average composition of the active hard solder, or braze, in the edge region; and heating the ceramic bodies, the active hard solder, or braze, and the solder stop in a vacuum soldering, brazing process, at least up to melting of the composition CM, wherein the melt in the edge region of the active hard solder, or braze, mixes with the material of the solder stop, whereby the melt in the edge region isothermally solidifies or becomes more viscous, and stops. Stopping means, in this connection, that a flowing of the active hard solder, or braze, to the extent that it happens, ceases in the edge region.
In a further development of the method, the active hard solder, or braze, comprises Zr, Ni and Ti.
In a further development of the invention, the composition CM0 of the active hard solder, or braze, comprises, before the joining, 20 atom-% to 24 atom-% Ni, 13 atom-% to 17 atom-% Ti, remainder Zr, wherein the composition CM comprises especially 63 atom-% Zr, 22 atom-% Ni and 15 atom-% Ti.
In a further development of the invention, the composition CE has, compared with the composition CM, thus, that of the main volume of the joint, after the joining, an increased Ni fraction.
In a further development of the invention, the solder stop is provided by depositing a metal or a mixture of various metals on at least one surface section of at least one ceramic body, wherein an enrichment of the metal or the mixture of metals in the active hard solder, or braze, leads to an increased liquidus temperature compared with the liquidus temperature of the composition of the main volume of the active hard solder, or braze.
In a further development of the invention, the deposited metal, respectively the mixture of deposited metals, contains nickel.
In a further development of the invention, the surface section of the ceramic body, in which the solder stop is provided, overlaps the contact surface between the joint and the ceramic body no more than 25%, preferably no more than 10%, of the contact surface between the joint and the ceramic body.